Uop/Fw Usa Solvent Deasphalting Process: Daniel B. Gillis

Source: HANDBOOK OF PETROLEUM REFINING PROCESSES
CHAPTER 10.4
UOP/FW USA SOLVENT DEASPHALTING PROCESS

Daniel B. Gillis
UOP LLC Des Plaines, Illinois
Fred M. Van Tine

Foster Wheeler USA Corporation Houston, Texas
INTRODUCTION
The UOP/FWUSA Solvent Deasphalting (UOP/FWUSA SDA) process is a solvent extraction process developed and jointly offered by UOP* and Foster Wheeler USA Corporation (FW) for the processing of vacuum residues (VR) or atmosphere residues (AR) feedstock. The UOP/FWUSA process contains process features from both UOPs Demex* solvent extraction process and FWs LEDA solvent deasphalting process. This combination of features has resulted in an advanced solvent deasphalting technology (UOP/FWUSA Solvent Deasphalting process) that is capable of achieving the highest product qualities with the lowest operating costs. The UOP/FWUSA SDA process employs a unique combination of features to separate VR into components whose uses range from incremental feedstock for downstream conversion units to the production of lube base stock and asphalts. Because the UOP/FWUSA process provides the refiner with increased flexibility regarding future processing decisions, including crude section, refinery debottlenecking, and the potential to reduce crude runs and fuel oil yields, it represents an important element in the refiners overall bottom-of-the-barrel processing strategy.
PROCESS DESCRIPTION
The UOP/FWUSA SDA process typically divides VR into two components: a relatively contaminant-free nondistillable deasphalted oil (DAO) and a highly viscous pitch. Like propane deasphalting, the UOP/FWUSA SDA process is based on the ability of light
*Trademark or service mark of UOP LLC.
10.37 Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright 2004 The McGraw-Hill Companies. All rights reserved. Any use is subject to the Terms of Use as given at the website.
UOP/FW USA SOLVENT DEASPHALTING PROCESS 10.38

SEPARATION PROCESSES
paraffin hydrocarbons to separate the residues heavier asphaltenic components. Associated with these heavier materials is the majority of the crudes contaminants. Consequently, the lower contaminant content of the recovered DAO allows this material to be used in many refining applications, probably the most important of which is as increment feedstock to catalytic processes such as fluid catalytic cracking (FCC) or hydrocracking for conversion into transportation fuel products. Because the pitch recorded from the UOP/FWUSA SDA unit contains most of the contaminants present in the crude, it typically has a high viscosity and a relatively low penetration value. Commercially, UOP/FWUSA SDA pitch has been used in the manufacturing of asphalts and cement and as a blending component in refinery fuel oil pools. Other potential uses include the production of hydrogen, synthesis gas, or low-Btu fuel gas and as a solid-fuel blending component. Unlike conventional propane deasphalting, the UOP/FWUSA SDA process uses a unique combination of heavier solvents, supercritical solvent techniques, and patented extractor internals to efficiently recover high-quality DAO at high yield. A schematic flow scheme of a modern UOP/FWUSA SDA design is shown in Fig. 10.4.1. This design, which has evolved from experience gained from both pilot-plant and commercial operations as well as detailed engineering analyses of its various components, minimizes operating and capital costs and efficiently recovers the desired product yields at the required product qualities. Incoming VR is mixed with solvent and fed to the vertical extractor vessel. At the appropriate extractor conditions, the VR-solvent blend is separated into its DAO and pitch components. The yield and quality of these components are dependent on the amount of contaminants in the feedstock, the composition and quantity of solvent used, and the operating conditions of the extractor. With the extractor, the downflowing asphaltene-rich pitch component and the upflowing DAO solvent mixture are separated by patented extractor internals. The extractor design also includes a unique liquid flow distribution system to minimize the possibility
FIGURE 10.4.1 Schematic flow diagram of UOP/FW USA SDA process.
Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright 2004 The McGraw-Hill Companies. All rights reserved. Any use is subject to the Terms of Use as given at the website.

10.39
of fouling the internals. Compared to previous designs, the increased separation efficiency achieved by these two features significantly reduces the size of the extractor vessel and the overall cost of the UOP/FWUSA SDA unit. The combination of heat exchange with recovered solvent and a direct-fired heater or a hot oil heating fluid heats the DAO solvent mixture leaving the top of the extractor to its critical temperature. The separation of the DAO and solvent components of this mixture is accomplished at supercritical conditions within the DAO separator. Recovered solvent is recycled back to the extractor. Because most of the solvent is recovered supercritically, this material can be effectively used for process heat exchange. Consequently, compared to earlier subcritical solvent-recovery designs, supercritical solvent recovery can reduce utilities requirements by more than one-third. To minimize solvent loss, any traces of solvent remaining in both the DAO exiting the DAO separator and the pitch from the extractor are recovered in the DAO and pitch strippers, respectively. This recovered solvent is also recycled to the extractor. If the recovery of an intermediate-quality resin stream is desiredfor instance, when specialty asphalts are produced or when independent control of DAO and pitch quality is desireda resin settler may be added between the units extractor and DAO separator.
TYPICAL FEEDSTOCKS
The SDA process (normally using propane or a propane-butane mixture as the solvent) has been in commercial use for the preparation of lubricant-bright-stock feeds from asphaltbearing crude residue for many years.8,9 Many commercial SDA units have also been used for preparing paving and specialty asphalts from suitable vacuum residues. The increasing use of the fluid catalytic cracking (FCC) process together with the increasing price of crude oil resulted in the need to maximize the quantity of FCC feedstock obtained from each barrel of crude. These conditions led to the extension of the SDA process to the preparation of cracking feedstocks from vacuum residues. The current trend for maximizing distillate oil production has also prompted the increased use of the SDA process to prepare hydrocracking feedstocks from vacuum residues. SDA supplements vacuum distillation by recovering additional high-quality paraffinic oil from vacuum residues beyond the range of practical distillation. Although atmospheric residues have been commercially solvent-deasphalted, typical SDA feedstocks are 570C (1060F ) TBP cut-point vacuum residues. These vacuum residues often contain high levels of metals (primarily nickel and vanadium), carbon residue, nitrogen, sulfur, and asphaltenes. Table 10.4.1 gives three examples of vacuum residue feedstocks, covering a wide range of properties, that can be processed in an SDA unit.
TABLE 10.4.1
Typical SDA Feedstocks Vacuum residue TBP cut point, C Gravity, API 3.6 8.1 11.7 Conradson carbon residue, wt % 25.1 17.4 15.0 Ni V, wt ppm 193 110 50
Sulfur, wt % 5.5 2.7 1.5
Heavy Arabian Heavy Canadian Canadian
570 570 570

PRODUCT YIELDS AND QUALITY

The VR fraction of a crude is the usual feedstock for the UOP/FWUSA SDA process. Typical properties of both the vacuum gas oil (VGO) and VR fractions of two common Middle Eastern crudes are presented in Table 10.4.2. As this table illustrates, the VR fraction contains virtually all the crudes asphaltenic (C7 insolubles) and organometallic (V Ni) contaminants and most of the crudes Conradson carbon residue. Each of these contaminants can significantly influence the choice of processing conditions and catalysts used in fixed-bed processing units. The UOP/FWUSA SDA process can be used to selectively reject the majority of these contaminants. Examples of DAO properties obtained at various extraction levels when processing the two Arabian-based VRs described in Table 10.4.2 are summarized in Tables 10.4.3 and 10.4.4. The selectivity of the process for contaminant rejection is illustrated by the absence of asphaltenes and the significantly reduced amounts of organometallics and Conradson carbon in the recovered DAO. These tables also illustrate that DAO quality decreases with increasing DAO yield. For the Arabian Light case, this decrease results in a variation in demetallization ranging from roughly 98 percent organometallic rejection at 40 percent DAO yield to approximately 80 percent rejection at 78 percent DAO yield. The same deterioration in DAO quality with increasing DAO yield is observed for the Arabian Heavy feed case. Estimated properties of the UOP/FWUSA SDA process pitches recovered from the two Arabian feedstock cases are presented in Tables 10.4.5 and 10.4.6. At the higher DAO recovery rates, these materials have zero penetration and can be blended with softer VRs to produce acceptable penetration-grade asphalts.
TABLE 10.4.2
Feedstock Properties Reduced crude VGO Vacuum residue
Feedstock
Arabian Light Cutpoint, C (F) Crude, LV % Specific gravity Sulfur, wt % Nitrogen, wt % Conradson carbon residue, wt % Metals (V Ni), wt ppm UOP K factor C7 insolubles, wt % Cutpoint, C (F) Crude, LV % Specific gravity Sulfur, wt % Nitrogen, wt % Conradson carbon residue, wt % Metals (V Ni), wt ppm UOP K factor C7 insolubles, wt % 343 (650 ) 38.8 0.9535 3.0 0.16 8.2 34 11.7 3.5 343566 (6501050) 26.3 0.9206 2.48 0.08 0.64 0 11.8 0 566 (1050 ) 12.5 1.0224 4.0 0.31 20.8 98 11.4 10
Arabian Heavy 343 (650 ) 53.8 0.9816 4.34 0.27 13.3 125 11.5 6.9 343566 (6501050) 30.6 0.9283 2.92 0.09 0.99 0 11.7 0 565 (1050 ) 23.2 1.052 6.0 0.48 27.7 269 11.3 15

10.41
TABLE 10.4.3
DAO Properties of Arabian Light DAO yield, LV % of vacuum residue 40 60 0.9638 2.83 0.15 7 6.36 11.7 78 0.9861 3.25 0.21 19 10.7 0.05 11.6
Specific gravity Sulfur, wt % Nitrogen, wt % Metals (V Ni), wt ppm Conradson carbon residue, wt % C7 insolubles, wt % UOP K factor
0.9406 2.34 0.1 3 2.85 11.9
TABLE 10.4.4
DAO Properties of Arabian Heavy DAO yield, LV % of vacuum residue 30 55 0.9861 4.29 0.2 38 10.1 0.05 11.8
Specific gravity Sulfur, wt % Nitrogen, wt % Metals (V Ni), wt ppm Conradson carbon residue, wt % C7 insolubles, wt % UOP K factor
0.9576 3.53 0.14 16 4.79 12.0
TABLE 10.4.5
Pitch Properties of Arabian Light SDA extraction level, LV % of vacuum residue 40 60 12.9 1.11 5.52 216 102 (215) 78 7.0 1.154 6.31 341 177 (368)
Yield, LV % of reduced crude Specific gravity Sulfur, wt % Metals (V Ni), wt ppm Softening point, C (F)
19.3 1.0769 4.96 154 88 (190)
Physical Properties DAO physical properties are affected as follows as the DAO yield increases: 1. Specific gravity. Specific gravity increases as DAO yield increases (DAO becomes heavier). See Table 10.4.7. 2. Viscosity. Viscosity increases as DAO yield increases (which corresponds to a heavier DAO). See Table 10.4.7. 3. Heptane insolubles. Content of heptane insolubles (asphaltenes) remains very low as DAO yield increases. Nevertheless, the asphaltenes content of the DAO will increase,

TABLE 10.4.6 Pitch Properties of Arabian Heavy SDA extraction level, LV % of vacuum residue 30 Yield, LV % of reduced crude Specific gravity Sulfur, wt % Metals (V Ni), wt ppm Softening point, C (F) 30.2 1.0925 6.93 364 104 (219) 55 19.4 1.1328 7.82 515 149 (300)
TABLE 10.4.7 DAO Properties
Solvent-Deasphalting Heavy Arabian Vacuum Residue: DAO yield, vol % on feed 15.1 20.3 183 82.5 54 0.01 47.4 14.6 599 132 32 0.01 65.3 10.8 1590 263 38 0.01 73.8 9.4 2540 432 41 0.03
Vacuum residue Gravity, API Viscosity at 100C, SSU Viscosity at 150C, SSU Pour point, C Heptane insolubles, wt % 3.6 70,900 3,650 74 16.2
Source: J. C. Dunmyer, Flexibility for the Refining Industry, Heat Eng., 5359 (OctoberDecember 1977).
approaching the feedstock asphaltene content as DAO yield approaches 100 percent. See Table 10.4.7. 4. Pour point. At low DAO yields the pour point is high, consistent with the paraffinic character of the DAO. As DAO yield increases, less paraffinic material is dissolved, which in many cases is reflected in a decreasing pour point. As DAO yield continues to increase, the pour point will ultimately near the feed pour point for DAO yields, approaching 100 percent. See Table 10.4.7.
Sulfur The sulfur distribution between the DAO and the pitch is a function of DAO yield. Figure 10.4.2 shows a typical relationship between the ratio of sulfur concentration in the DAO to sulfur concentration in the feed as a function of DAO yield. This figure shows an average sulfur distribution trend and also maximum and minimum ranges expected for a wide number of vacuum residue feedstocks. For a specific feedstock, the sulfur distribution relationship is close to linear, especially as DAO yield increases above 50 vol %.18,19 The ability of a solvent to reject the feedstock sulfur into the asphalt selectively is not as pronounced as its ability to reject metal contaminants such as nickel and vanadium selectively.16 This is illustrated in Fig. 10.4.6. The sulfur atoms are more evenly distributed between the paraffinic and aromatic molecules than the metal contaminants, which are heavily concentrated in the aromatic molecules. In many cases, the fact that the metal content in the DAO is low makes hydrodesulfurization of high-yield DAO technically feasible and economically attractive.

10.43
FIGURE 10.4.2 Ratio of sulfur concentration in DAO to sulfur concentration in the feedstock versus DAO yield.
Nitrogen Figure 10.4.3 shows the ratio of the nitrogen in the DAO to the nitrogen in the feed as a function of DAO yield. It shows the average nitrogen distribution trend and the maximum and minimum expected for a wide variety of vacuum residue feedstocks. As shown by a straight line on a semilog plot, this relationship is exponential. Figure 10.4.3 shows that there is little difference among various vacuum residues in the solvents ability to reject nitrogen into the asphalt selectively. The difference between the maximum and minimum expected values is significantly lower than in the sulfur distribution plot (Fig. 10.4.2). SDA exhibits a better ability to reject selectively nitrogen-containing compounds than sulfur-containing compounds.1,16 (See Fig. 10.4.6.)
Metals The ratio of DAO metal content (Ni V) to feedstock metal content as a function of DAO yield is shown in Fig. 10.4.4. The straight lines in the figure show that DAO metals content is an exponential function of DAO yield. This trend has been previously reported.1,16 Figure 10.4.4 also shows that metal distribution is a strong function of the feedstock API gravity. The data in the figure illustrate an average relationship; however, some feedstocks such as Canadian sour and Tia Juana vacuum residues deviate substantially from the average trend. Pilot-plant data are normally required to determine the exact DAO yield-quality relationship for a previously untested feedstock. The nickel and vanadium distributions between the DAO and asphalt are similar but not equal.16 (See Fig. 10.4.6.) Figure 10.4.4 shows that metals are rejected from DAO to a

FIGURE 10.4.3 Ratio of nitrogen concentration in DAO to nitrogen concentration in the feedstock versus DAO yield.
FIGURE 10.4.4 Ratio of metal (Ni feedstock versus DAO yield.
V) concentration in DAO to metal (Ni
V) concentration in the

10.45
much greater extent than sulfur and nitrogen. For example, in deasphalting heavy Arabian vacuum residue at a 65 vol % DAO yield, the following are the ratios of the contaminant level in the DAO to the contaminant level in the feedstock: Sulfur Nitrogen Nickel Vanadium CCR 72.7% 50.0% 13.8% 16.3% 49.0%
The high rejection of metals from DAO is of extreme importance in the catalytic processing of DAO. It is possible catalytically to hydroprocess DAO economically owing to the low metals content of DAO obtained even from a high-metal-content vacuum residue.
Conradson Carbon Residue The deasphalting solvent exhibits a moderate selectivity for carbon rejection from DAO; the selectivity is similar to that of nitrogen rejection but significantly higher than that of sulfur rejection. Conradson carbon residue* (CCR) in DAO has a less detrimental effect on the cracking characteristics of DAO than it has in the case of distillate stocks.4 DAO with 2 wt % CCR is an excellent FCC feedstock; it actually produces less coke and more gasoline than coker distillates. Figure 10.4.5 shows that the ratio of CCR in DAO to CCR in the feed is an exponential function of DAO yield. As in the case of metals concentrations, the relationship is also a strong function of feedstock API gravity. The data in Fig. 10.4.5 illustrate an average relationship for a number of feedstocks and should not be considered a design correlation. As in the case of metals, some feedstocks, such as Canadian sour and Tia Juana, deviate substantially from the average trend. See also Fig. 10.4.6.
PROCESS VARIABLES
Several process variables affect the yield and quality of the various products. These variables include extraction pressure and temperature, solvent composition, and extraction efficiency.
Extraction Pressure and Temperature Extraction pressure, which is chosen to ensure that the SDA extractors solvent-residue mixture is maintained in a liquid state, is related to the critical pressure of the solvent used.
*Conradson carbon residue is a standard test (ASTM D 189) used to determine the amount of residue left after evaporation and pyrolysis of an oil sample under specified conditions. The CCR is reported as a weight percent. It provides an indication of the relative coke-forming propensities of an oil sample.

FIGURE 10.4.5 DAO yield.
Ratio of CCR in DAO to CCR in feedstock versus
FIGURE 10.4.6 Selectivity in solvent deasphalting. [Courtesy of the Gulf Publishing Company, publishers of Hydrocarbon Processing, 52(5), 110113 (1973).]

10.47
During normal operation, when both the extraction pressure and solvent composition are fixed, SDA product yields and qualities are controlled by adjusting the extractor temperature. This adjustment is achieved by varying the temperature of the recycled solvent stream. Increasing the temperature of this stream reduces the solubility of the residues heavier components and improves DAO quality at the expense of reduced DAO yield. Extraction temperature must be maintained below the critical temperature of the solvent, however, because at higher temperatures no portion of the residue is soluble in the solvent and no separation occurs.
Solvent Composition Solvents typically used in the UOP/FWUSA SDA process include components such as propane, butanes and pentanes, and various mixtures of these components. Because these materials are generally readily available within a refinery, their use is relatively inexpensive. In addition, because the majority of the solvent is recirculated within the unit, solvent makeup rates are relatively small. Increasing the solvents molecular weight increases the yield of recovered DAO by allowing more of the heavier, more-resinous components of the feedstock to remain in the DAO. At the same time, however, the quality of the DAO decreases because these heavier materials have higher contaminant levels. Consequently, proper solvent selection involves balancing increased product yield and decreased product quality. Generally, light solvents, such as propane, are specified when the highest DAO quality is desired. However, light solvents typically produce low DAO yields. Intermediate solvents, such as butanes, are used when a reasonably high yield of high-quality DAO is desired. Finally, heavier solvents, such as pentanes, are used when the maximum yield of DAO is desired, for instance, when the DAO is to be hydrotreated before further processing.
Extraction Efficiency The separation efficiency of the DAO and pitch products is significantly influenced by the amount of solvent that is mixed with the incoming feed to the SDA extractor. Increasing the amount of solvent improves the separation and produces a higher-quality DAO. Figure 10.4.7 illustrates the impact of solvent rate on DAO quality. In this example, a DAO containing 40 wt ppm organometallics is recovered at a 3:1 solvent/oil (S:O) ratio for 50 vol % DAO yield. When the same feedstock is processed at a higher 5:1 S:O, the organometallic content of the DAO recovered at the same 50 vol % DAO yield is reduced to 30 wt ppm. Unfortunately, because the quantity of solvent recirculated within the unit is significantly greater than the amount of feedstock being processed, the improved DAO quality achievable at higher solvent rates must be balanced against the additional operating costs associated with the higher solvent recirculation and solvent recovery requirements and the increased capital costs associated with the larger equipment sizes. In Fig. 10.4.7, the improvement in DAO quality must be balanced against the roughly 50 percent higher operating and capital costs associated with the higher solvent recirculation rate. The addition of patented UOP/FWUSA SDA extractor internals, however, modifies the relationship between DAO yield and DAO quality by improving the extractors separation efficiency. As shown in Fig. 10.4.7, the internals may be used to offset higher solvent recirculation rates by allowing either higher-quality DAO to be recovered at the same DAO yield or, conversely, more DAO to be recovered at the same DAO quality. Also, the additional operating and capital costs associated with higher solvent recirculation rates are eliminated when the intervals are employed.

FIGURE 10.4.7
Effect of solvent rate and extractor internals.
EXTRACTION SYSTEMS
The efficiency of the SDA process is highly dependent on the performance of the liquidliquid extraction device. Proper design of the extraction device is necessary to overcome the mass-transfer limitations inherent in processing heavy, viscous oils to ensure that the maximum yield of a specified quality of DAO is obtained. There are two major categories of extraction devices used for solvent deasphalting: mixer-settlers (a single stage or several stages in series) and countercurrent (multistage) vertical towers.
Mixer-Settler Extraction Mixer-settlers were the first SDA devices used commercially, and this is the simplest continuous-extraction system.10 It consists of a mixing device (usually an in-line static mixer or a valve) for intimately mixing the feedstock and the solvent before this mixture flows to a settling vessel. The settling vessel has sufficient residence time to allow the heavy pitch (raffinate) phase to settle by gravity from the lighter solvent-oil phase (extract). A single-stage mixer-settler results in, at best, one equilibrium extraction stage, and therefore the separation between the DAO and pitch is poorer than that obtainable with a countercurrent multistage extraction tower. This poorer separation is evidenced by the higher nickel and vanadium content of the DAO produced by the single-stage system compared to the multistage system. Table 10.4.8 gives data comparing the DAO obtained from Kuwait vacuum residue by using one equilibrium extraction stage versus that obtained from a countercurrent multistage extraction.11 These data were obtained at a solvent/feed ratio of 6:1. Single-stage mixer-settler extraction devices were gradually replaced by vertical countercurrent towers as the advantage of multistage countercurrent extraction became evident. The economic incentive for obtaining the maximum yield of high-quality DAO for lubricant production has resulted in the use of multistage countercurrent extraction towers in virtually all lubricating oil refineries. Recently, some SDA designers have advocated a return to the mixer-settler extraction system for processing vacuum residues to obtain cracking feedstock, a considerably lower-value product than lubricating oil bright stock. This position is based on the theory that

10.49
TABLE 10.4.8 Solvent-Deasphalting Kuwait Vacuum Residue % of Feed (Ni Pitch product, vol % on crude 8 10 12 Single-stage 22 17 13 V) in DAO Multistage countercurrent 8 4.5 2
Source: C. G. Hartnett, Some Aspects of Heavy Oil Processing, API 37th Midyear Meeting, New York, May 1982.
the lower installed cost of the mixer-settler system offsets the product value loss due to the lower DAO yield. This is true only for low marginal values of the DAO cracking stock over the vacuum residue feedstock and for small yield losses. The latter assumption is true at very high (in general, greater than 90 vol %) DAO yields. With the heavier crudes being processed today, this is not always a realistic assumption.
Countercurrent Extraction As shown in Table 10.4.8, countercurrent extraction provides a much more effective means of separation between the DAO and the asphalt than does single-stage mixer-settler extraction. This subsection will discuss the major factors affecting the design of a commercial countercurrent SDA extraction tower. Countercurrent contact of feedstock and extraction solvent is provided in an extraction vessel called a contactor or extractor tower. Liquid solvent (light phase) enters the bottom of the extraction tower and flows upward as the continuous phase. The vacuum residue feedstock enters the upper section of the extraction tower and is dispersed by a series of fixed or rotating baffles into droplets which flow downward by gravity through the rising continuous solvent phase. As the droplets descend, oil from the droplets dissolves into the solvent, leaving insoluble asphalt or resin, saturated with solvent, in the droplets. These droplets collect and coalesce in the bottom of the tower and are continuously withdrawn as the asphalt phase (heavy phase, or raffinate). As the continuous solvent phase, containing the dissolved DAO, reaches the top of the tower, it is heated, causing some of the heavier, more aromatic dissolved oil to separate from the solution. These heavier liquid droplets flow downward through the ascending continuous solvent-DAO solution and act as a reflux to improve the sharpness of the separation between the DAO and the asphalt. This type of extraction system is analogous to the conventional distillation process. The most common extractor towers used commercially are the rotating-disk contractor (RDC) and the fixed-element, or slat, towers. RDCs have proved to be superior to slat towers because of the increased flexibility inherent in their operation as well as the improved DAO quality obtained by using the RDC.12 A 3 to 5 percent DAO-yield advantage has been found for the RDC at constant DAO quality.10,12 More recently, structured packing has been used in place of slats or RDCs for extractor internals. Due to the high efficiency of structured packing, the extractor sizes have been reduced for the same feed rates. Figure 10.4.8 shows a schematic of a rotating-disk contactor. The RDC consists of a vertical vessel divided into a series of compartments by annular baffles (stator rings) fixed

FIGURE 10.4.8 Rotating-disk contactor.
to the vessel shell. A rotating disk, supported by a rotating shaft, is centered in each compartment. The rotating shaft is driven by a variable-speed drive mechanism through either the top or the bottom head of the tower. Steam coils are provided in the upper section of the tower to generate an internal reflux. Calming grids are provided at the top and bottom sections of the tower. The number of compartments, compartment dimensions, location of

10.51
the feed nozzle, and rotor speed range are all selected to provide optimal performance for a given set of operations.
RDC Capacity The conditions under which flooding occurs in an RDC or slat tower represent the capacity limit at which the contactor can be operated. Flooding is evidenced by a loss of the interface level between the solvent and the pitch phases in the bottom of the tower as well as by a deterioration in DAO quality. Usually this condition will appear quite suddenly, and if it is not properly corrected, pitch may be entrained into the DAO recovery system. The maximum capacity of an RDC tower is a function of the energy input of the rotating disk. This energy input is given by the following equation.12,13 E N 3R5 HD2
where D E H N R
tower diameter, ft energy input factor, ft2/s3 compartment height, ft rotor speed, r/s rotor-disk diameter, ft
The tower capacity is given by the quantity T VD CR VC
where VC VD CR O T
superficial velocity of solvent (continuous phase), ft/h superficial velocity of residue (dispersed phase), ft/h factor, defined by RDC internal geometry14; it can be taken as the smaller value of O2/D2 or (D2 R2) /D2 diameter of opening in stator, ft tower capacity, ft/h
For a fixed RDC internal geometry and for a given system (at constant solvent/feed ratio) the quantity VD VC at flooding (maximum tower capacity) is a smooth function of energy input quantity E. This function is illustrated by Fig. 10.4.9 for propane deasphalting in lubricating oil manufacture. This type of correlation permits the scaling up of pilotplant data to a commercial-size unit or recalculation of the capacity of an existing tower for the same system at different conditions.
RDC Temperature Gradient It is possible to improve the quality of the DAO product at a constant DAO yield by maintaining a temperature gradient across the extraction tower. A higher temperature at the top of the RDC as compared with the bottom generates an internal reflux because of the lower solubility of oil in the solvent at the top compared with the bottom. This internal reflux supplies part of the energy for mixing and increases the selectivity of the extraction process in a manner analogous to reflux in a distillation tower.

FIGURE 10.4.9 RDC capacity for propane deasphalting. [Courtesy of Pennwell Publishing Company, publishers of the Oil and Gas Journal, 59, 9094 (May 8, 1961).]
Table 10.4.9 illustrates the effect of the RDC temperature gradient on the extraction process. Note that the RDC top temperature has been held constant and that the DAO yield is essentially unchanged.
RDC Rotor Speed The RDC rotor speed has a significant effect on the yield and properties of the DAO and asphalt products. With all other variables held constant, an increase in rotor revolutions per minute within a certain speed range can result in an increased DAO yield. This yield increase is the direct result of higher mass-transfer rates when rotor speed is increased. The effect of rotor speed on product yields and product properties is more evident at low throughputs and low rotor rates. At high throughputs much of the energy of mixing is obtained from the counterflowing phases themselves; in this case low rotor rates are sufficient to bring the extraction system up to optimal efficiency. Table 10.4.10 illustrates the effect of rotor speed on a low-throughput operation. Note that the DAO yield is increased with little deterioration of DAO quality.
DAO PROCESSING
Because the most common application of the UOP/FWUSA SDA process involves recovering additional feedstock for catalytic processes such as FCC or hydrocracking, the amount of DAO recovered in the SDA unit can have a significant impact on the quantity and quality of the feedstock used in the conversion unit. Figures 10.4.10 and 10.4.11 summarize the Conradson carbon and organometallic contents of the VGO-DAO blends produced at various DAO recovery rates when processing the Arabian Light and Arabian Heavy feedstocks, respectively. Figure 10.4.10 indicates that processing the Arabian Light feedstock at DAO recovery rates as high as 78 percent produces VGO-DAO blends with contaminant levels within typical FCC and hydrocracking feedstock specifications. Consequently, the inclusion of the

10.53
TABLE 10.4.9
Effect of RDC Temperature Gradient on DAO Quality DAO properties
RDC temperature gradient, C 14 23
DAO yield on feed, vol % 83.0 83.3
API 22.3 23.4
Ni, wt ppm 0.75 0.50
V, wt ppm 0.55 0.40
Source: R. J. Thegze, R. J. Wall, K. E. Train, and R. B. Olney, Oil Gas J., 59, 9094 (May 8, 1961).
TABLE 10.4.10
Effect of RDC Rotor Speed on Extraction Process DAO properties
RDC rotor speed, r/min 20 35 50
DAO yield of feed, vol % 76.8 80.3 83.3
Viscosity, SSU at 100C 194 198 203
Gravity, API 23.2 23.0 22.3
CCR, wt % 1.4 1.5 1.5
Asphalt penetration, 0.1 mm at 25C 38 8 1
Source: R. J. Thegze, R. J. Wall, K. E. Train, and R. B. Olney, Oil Gas J., 59, 9094 (May 8, 1961).
FIGURE 10.4.10 VGO-DAO blend quality (Arabian Light case).

FIGURE 10.4.11
VGO-DAO blend quality (Arabian Heavy case).
UOP/FWUSA SDA unit increased the amount of feedstock used by the conversion unit by approximately 35 percent. Figure 10.4.11 indicates that a similar percentage increase in conversion unit feedstock is obtained from the Arabian Heavy feedstock when producing a comparable VGO-DAO quality. Because of the higher contaminant content of the Arabian Heavy crude, however, this VGO-DAO quality limit is reached at a lower DAO recovery rate. Thus, hydrotreating DAO recovered from highly contaminated crudes may be an economically feasible bottom-of-the-barrel processing strategy.
PITCH PROPERTIES AND USES

The pitch yield decreases with increasing DAO yield, and the properties of the pitch are affected as follows:22

Specific gravity increases, corresponding to a heavier material. Softening point increases, and penetration decreases. Sulfur content increases. Nitrogen content increases.
Table 10.4.11 gives pilot-plant data which illustrate the trend of pitch properties with decreasing pitch yield. Since SDA preferentially extracts light and paraffinic hydrocarbons,3,23 the resulting asphalt is more aromatic than the original feed. Further, note that high-softening-point

10.55
TABLE 10.4.11
Solvent-Deasphalting Heavy Arabian Vacuum Residue Pitch Fraction Vacuum residue feed Asphalt yields, vol % 84.9 1.0679 79 9 5.9 0.53 71.8 52.6 1.1185 128 0 6.6 0.65 26.8 44 1.1290 139 0 7.3 0.73 34.7 1.1470 164 0 7.9 0.79 45.1 26.2 1.1690 0 8.2 0.97 80.2
Specific gravity, 60F/60F Softening point (R&B), C Penetration at 25C, 0.1 mm Sulfur, wt % Nitrogen, wt % Heptane, insoluble, wt %
1.0474 62 24 5.5 0.46 14.1
Source: J. C. Dunmyer, Flexibility for the Refining Industry, Heat Eng., 5359 (OctoberDecember 1977).
(greater than 105 to 120C) asphaltenes are free of wax even when precipitated from very waxy residues.24 Except for SDA units specifically designed to produce roofing or paving asphalt, the asphalt product is normally considered a low-value by-product. Since there is a very limited commercial market for these by-product asphalts, the refiner must usually find some method of disposing of the asphalt by-product other than by direct sale. The following are the main uses of the asphalt fraction.
Fuel In some cases, pitch can be cut back with distillate materials to make No. 6 fuel oil. Catalytic cycle oils and clarified oils are excellent cutter stocks. When low-sulfur-content fuels are required and when the original deasphalter feedstock is higher in sulfur, direct blending of the asphalt to make No. 6 fuel oil generally is not possible. Relatively low-softening-point pitch can be burned directly as refinery fuel, thereby avoiding the need to blend the pitch with higher-value cutter stocks. Direct pitch burning has been practiced in a number of refineries. However, the highsulfur-content crudes currently being processed by many refineries result in a high-sulfurcontent pitch which cannot be burned directly as refinery fuel unless a stack-gas sulfur oxide removal process is used to meet U.S. environmental regulations. It is possible to use solid (flaked or extruded) pitch as fuel for public utility power plants in conventional boilers with stack-gas cleanup or in modern fluidized-bed boilers.25 These boilers use fluidized limestone beds directly to capture metals and sulfur oxides from the combustion gases.
Commercial Asphalts Commercial penetration-grade asphalts can be produced by simply blending SDA pitch with suitable aromatic flux oils. In many cases, this can eliminate the need for air-oxidizing asphalts and thus present obvious economic and environmental advantages. When SDA pitch (which are wax-free) are blended with a nonparaffinic flux oil, asphalts having satisfactory ductility can be made even from waxy crudes.3 This eliminates the need to buy special crudes for asphalt manufacture.

Partial Oxidation Pitch can be used as a feedstock for synthesis-gas manufacture in partial-oxidation units. This synthesis gas can be used to produce hydrogen for the refinery hydroprocessing units, thereby eliminating the need to steamreform more valuable distillate oils or natural gas to produce hydrogen.
INTEGRATION OF SDA IN MODERN REFINERIES

Selection of the optimum residue-upgrading route depends on many factors, such as

Available feedstock characteristics Required flexibility for processing different feedstock Feedstock cost Product markets Product values Existing refinery configuration and possibility for process-unit integrations Operating costs Unit capital investment costs Unit stream factors
Typically, optimization studies use linear programming techniques. This optimization is performed during the initial refinery-expansion study phase to determine the most economical conversion route. For the purpose of illustrating the integration of SDA units in bottom-of-the-barrel upgrading, a refinery processing 50,000 BPSD of Kuwait atmospheric residue was selected. The following processing routes are considered: Base Refinery. (See Fig. 10.4.12.) The basic processing route uses a conventional vacuum-flasher scheme together with vacuum gas oil (VGO) hydrotreating (hydrodesulfurization, or HDS) followed by fluid catalytic cracking. This basic refinery scheme does not provide any vacuum residue upgrading. The block flow diagram given in Fig. 10.4.12 summarizes the expected product yields when processing 50,000 BPSD of Kuwait atmospheric residue. The products include 20,000 BPSD of heavy, high-sulfur vacuum residue. The main products are summarized in Table 10.4.12. Maximum-Naphtha Case. (See Fig. 10.4.13.) This processing route is similar to the base refinery, but an SDA unit, which produces additional FCC unit feedstock from the vacuum residue, has been included. The major change is that instead of the basecase 20,000-BPSD vacuum residue production, 5400 BPSD of asphalt is produced. Table 10.4.12 summarizes the main products and shows that naphtha production has been increased by 49 percent with respect to the base case. For this illustration FCC was used for the VGO-DAO conversion, although hydrocracking also can be an economically viable route. Maximum-Distillate Case. In this processing scheme the DAO together with the VGO is cracked in a hydrocracking unit. Figure 10.4.14 shows the flow scheme for this processing route, and Table 10.4.12 summarizes the main products. This table

10.57
FIGURE 10.4.12 Integration of SDA in modern refineries: base refinery (no SDA unit provided).
TABLE 10.4.12
Integration of SDA in Refineries SDA unit application Base refinery Maximum naphtha 8,054 23,315 14,659 5,400* Maximum distillates 1,383 8,563 40,407 5,400* Maximum low-sulfur fuel oil 289 388 4,090 46,051
Products, BPSD: C3-C4 LPG Naphtha Distillates Fuel oil Asphalt Fuel oil quality API wt % sulfur
5,410 15,680 9,858 20,000* 5.6 5.55
19.4 1.55
*Outside No. 6 fuel-oil specifications.
shows that the naphtha yield was reduced by 50 percent and the distillate yields (jet fuel plus diesel) increased by 400 percent relative to the base case. Maximum Low-Sulfur Fuel Oil. Maximum fuel oil production is not the general trend in the refinery industry but could be economically attractive under certain market conditions. This processing route is shown in Fig. 10.4.15. In this case the DAO together with the VGO is hydrotreated (HDS) and blended with the asphalt to produce a 1.55 percent sulfur fuel oil. This product corresponds to a 60 percent desulfurization of the atmospheric residue. Compared with direct desulfurization of the atmospheric residue, this route can be economically attractive in many cases.

FIGURE 10.4.13
Integration of SDA in modern refineries: maximum naphtha case.
FIGURE 10.4.14
Integration of SDA in modern refineries: maximum distillate case.
Desulfurization of the DAO plus the VGO blend is a simpler, less expensive process than direct atmospheric-residue hydrotreating. Lubricating Oil Production. For many years SDA has been used in the manufacture of lubricating oils. In this case SDA produces a short DAO cut, which is further treated (typically by furfural and then dewaxed) to produce high-quality lubricating oil

10.59
FIGURE 10.4.15 Integration of SDA in modern refineries: maximum low-sulfur fuel oil case.
base stocks. Older processing schemes would typically include solvent (Furfural or NMP) extraction followed by solvent dewaxing. More recent schemes would typically include hydrotreating followed by either solvent dewaxing or catalytic dewaxing, if a wax product is not required. (Fig. 10.4.16).
PROCESS ECONOMICS
The estimated battery-limits cost for a nominal 20,000 BPSD two-product UOP/FWUSA SDA unit constructed to UOP/FWUSA standards, second quarter of 2002, at a U.S. Gulf Coast location is approximately $24 million. The UOP/FWUSA SDA process can have a wide range of utility consumptions depending on

Solvent/oil ratio Solvent type Feed and product temperatures DAO yield Degree of heat recovery with the supercritical heat exchangers
However, for a typical application, based on supercritical solvent recovery and a 5:1 solvent/oil ratio, the utilities per barrel of feed are Fuel, 56 MBtu Power, 1.8 kWh Medium-pressure steam, 11 lb Collectively UOP and FWUSA have licensed and designed over 50 SDA units and have experience in every application of solvent deasphalting. Symbols and abbreviations used in the chapter are listed in Table 10.4.13.

FIGURE 10.4.16
Integration of SDA in modern refineries: lubricating oil production case.
TABLE 10.4.13 API
Abbreviations LP LPG MP N Ni O PVHE R R&B S SCFD SDA sp gr SSU TBP TC V VC VD Low pressure Liquefied petroleum gas Medium pressure Rotor speed, r/s Nickel Diameter of stator opening, ft Pressure vapor heat exchanger Rotor-disk diameter, ft Ring and ball (softening point) Sulfur Standard cubic feet per day Solvent deasphalting Specific gravity at 60F/60F Seconds Saybolt universal (viscosity) True boiling point Temperature controller Vanadium Solvent superficial velocity, ft/h Residue superficial velocity, ft/h
bbl BPSD CCR CR C CWR CWS DAO D D&E E F FC FCC H HDS HP LC
Degrees on American Petroleum Institute scale: API (141.5/sp gr) 131.5 Barrel (42 U.S. gal) Barrels per stream-day Conradson carbon residue Factor defined by tower internal geometry Degrees Celsius Cooling-water return Cooling-water supply Deasphalted oil Tower diameter, ft Delivered and erected (cost) Energy input factor, ft2/s3 Degrees Fahrenheit Flow controller Fluid catalytic cracker Compartment height, ft Hydrodesulfurization High pressure Level controller
REFERENCES
1. J. A. Bonilla, Delayed Coking and Solvent Deasphalting: Options for Residue Upgrading, AIChE National Meeting, Anaheim, Calif., June 1982. 2. W. J. Rossi, B. S. Deighton, and A. J. MacDonald, Hydrocarb. Process., 56(5), 105110 (1977). 3. J. G. Ditman and J. P. Van Hook, Upgrading of Residual Oils by Solvent Deasphalting and Delayed Coking, ACS Meeting, Atlanta, April 1981. 4. P. T. Atteridg, Oil Gas J., 61, 7277 (Dec. 9, 1963).

10.61
5. J. G. Ditman and R. L. Godino, Hydrocarb. Process., 44(9), 175178 (1965). 6. J. C. Dunmyer, R. L. Godino, and A. A. Kutler, Propane Extraction: A Way to Handle Residue, Heat Eng. (NovemberDecember 1966). 7. R. L. Godino, Propane Extraction, Heat Eng. (MarchApril 1963). 8. J. G. Ditman and F. T. Mertens, Pet. Process. (November 1952). 9. A. Rhoe, Meeting the Refiners Upgrading Needs, NPRA Annual Meeting, San Francisco, March 1983. 10. S. Marple, Jr., K. E. Train, and F. D. Foster, Chem. Eng. Prog., 57(12), 4448 (1961). 11. C. G. Hartnett, Some Aspects of Heavy Oil Processing, API 37th Midyear Meeting, New York, May 1982. 12. R. J. Thegze, R. J. Wall, K. E. Train, and R. B. Olney, Oil Gas J., 59, 9094 (May 8, 1961). 13. G. H. Reman and J. G. van de Vusse, Pet. Refiner, 34(9), 129134 (1955). 14. G. H. Reman, Pet. Refiner, 36(9), 269270 (1957). 15. J. W. Gleitsmann and J. S. Lambert, Conserve Energy: Modernize Your Solvent Deasphalting Unit, Industrial Energy Conservation Technology Conference, Houston, April 1983. 16. J. G. Ditman, Hydrocarb. Process., 52(5), 110113 (1973). 17. S. R. Sinkar, Oil Gas J., 72, 5664 (Sept. 30, 1974). 18. J. G. Ditman, Solvent DeasphaltingA Versatile Tool for the Preparation of Lube Hydrotreating Feed Stocks, API 38th Midyear Meeting, Philadelphia, May 17, 1973. 19. D. A. Viloria, J. H. Krasuk, O. Rodriguez, H. Buenafama, and J. Lubkowitz, Hydrocarb. Process., 56(3), 109113 (1977). 20. J. C. Dunmyer, Flexibility for the Refining Industry, Heat Eng., 5359 (OctoberDecember 1977). 21. E. E. Smith and C. E. Fleming, Pet. Refiner, 36, 141144 (1957). 22. H. N. Dunning and J. W. Moore, Pet. Refiner, 36, 247250 (1957). 23. J. G. Ditman and J. C. Dunmyer, Pet. Refiner, 39, 187192 (1960). 24. J. G. Ditman, Solvent Deasphalting for the Production of Catalytic CrackingHydrocracking Feed & Asphalt, NPRA Annual Meeting, San Francisco, March 1971. 25. R. L. Nagy, R. G. Broeker, and R. L. Gamble, Firing Delayed Coke in a Fluidized Bed Steam Generator, NPRA Annual Meeting, San Francisco, March 1983.

Uop/Fw Usa Solvent Deasphalting Process: Daniel B. Gillis

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Uop/Fw Usa Solvent Deasphalting Process: Daniel B. Gillis

Uploaded by

Copyright:

Available Formats

Source: HANDBOOK OF PETROLEUM REFINING PROCESSES

UOP/FW USA SOLVENT DEASPHALTING PROCESS

Fred M. Van Tine

*Trademark or service mark of UOP LLC.

UOP/FW USA SOLVENT DEASPHALTING PROCESS 10.38

FIGURE 10.4.1 Schematic flow diagram of UOP/FW USA SDA process.

UOP/FW USA SOLVENT DEASPHALTING PROCESS

Sulfur, wt % 5.5 2.7 1.5

Heavy Arabian Heavy Canadian Canadian

570 570 570

UOP/FW USA SOLVENT DEASPHALTING PROCESS 10.40

PRODUCT YIELDS AND QUALITY

Feedstock Properties Reduced crude VGO Vacuum residue

UOP/FW USA SOLVENT DEASPHALTING PROCESS

0.9406 2.34 0.1 3 2.85 11.9

0.9576 3.53 0.14 16 4.79 12.0

19.3 1.0769 4.96 154 88 (190)

UOP/FW USA SOLVENT DEASPHALTING PROCESS 10.42

TABLE 10.4.7 DAO Properties

UOP/FW USA SOLVENT DEASPHALTING PROCESS

UOP/FW USA SOLVENT DEASPHALTING PROCESS 10.44

FIGURE 10.4.4 Ratio of metal (Ni feedstock versus DAO yield.

V) concentration in DAO to metal (Ni

UOP/FW USA SOLVENT DEASPHALTING PROCESS

UOP/FW USA SOLVENT DEASPHALTING PROCESS 10.46

FIGURE 10.4.5 DAO yield.

Ratio of CCR in DAO to CCR in feedstock versus

UOP/FW USA SOLVENT DEASPHALTING PROCESS

UOP/FW USA SOLVENT DEASPHALTING PROCESS 10.48

Effect of solvent rate and extractor internals.

UOP/FW USA SOLVENT DEASPHALTING PROCESS

UOP/FW USA SOLVENT DEASPHALTING PROCESS 10.50

FIGURE 10.4.8 Rotating-disk contactor.

UOP/FW USA SOLVENT DEASPHALTING PROCESS

The tower capacity is given by the quantity T VD CR VC

UOP/FW USA SOLVENT DEASPHALTING PROCESS 10.52

UOP/FW USA SOLVENT DEASPHALTING PROCESS

Effect of RDC Temperature Gradient on DAO Quality DAO properties

RDC temperature gradient, C 14 23

DAO yield on feed, vol % 83.0 83.3

API 22.3 23.4

Ni, wt ppm 0.75 0.50

V, wt ppm 0.55 0.40

Effect of RDC Rotor Speed on Extraction Process DAO properties

RDC rotor speed, r/min 20 35 50

DAO yield of feed, vol % 76.8 80.3 83.3

Viscosity, SSU at 100C 194 198 203

Gravity, API 23.2 23.0 22.3

CCR, wt % 1.4 1.5 1.5

Asphalt penetration, 0.1 mm at 25C 38 8 1

FIGURE 10.4.10 VGO-DAO blend quality (Arabian Light case).

UOP/FW USA SOLVENT DEASPHALTING PROCESS 10.54

VGO-DAO blend quality (Arabian Heavy case).

PITCH PROPERTIES AND USES

UOP/FW USA SOLVENT DEASPHALTING PROCESS

1.0474 62 24 5.5 0.46 14.1

UOP/FW USA SOLVENT DEASPHALTING PROCESS 10.56

INTEGRATION OF SDA IN MODERN REFINERIES

UOP/FW USA SOLVENT DEASPHALTING PROCESS

5,410 15,680 9,858 20,000* 5.6 5.55

*Outside No. 6 fuel-oil specifications.

UOP/FW USA SOLVENT DEASPHALTING PROCESS 10.58